Organic Electroluminescent Device

ABSTRACT

An organic electroluminescence device of the present invention adapts a new concept in its configuration to improve its efficiency in addition to obtain a high reliability and good yielding. The organic electroluminescent device having an electroluminescent film containing an organic material capable of causing an electroluminescence and being arranged between a first electrode and a second electrode, includes: a carrier generation layer, which is a floating electrode, is embodied in the electroluminescent film; an insulting film between the first electrode and the electroluminescent film, and an insulating film between the second electrode and the electroluminescent film, wherein the organic electroluminescent device is driven by an alternating current bias.

This application is a continuation of copending U.S. application Ser.No. 10/628,701, filed on Jul. 28, 2003.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an organic electroluminescent devicehaving an organic compound layer that generates light upon applicationof an electric field. More particularly, the present invention relatesto an organic electroluminescent device that emits light usingalternating current bias.

2. Description of the Related Art

Compared to inorganic compounds, organic compounds have more variousmaterial systems and possibilities for synthesizing organic materials tohave advanced various functions through appropriate molecular design.Further, things made from the organic compound have characteristics ofbeing flexible, and moreover, having workability by polymerization. Inlight of these advantages, in recent years, the technique of photonicsand electronics employing functional organic materials have beenattracted attention.

The technique of photonics utilizing optical properties of organicmaterials has already played an important role in contemporaryindustrial technology. For example, photosensitive materials such as aphotoresist have become indispensable for a photolithography techniquethat is used for the micro machining of semiconductors. In addition,since the organic compounds themselves have properties of lightabsorption and light emission caused by the light absorption(fluorescence or phosphorescence), they are also well suited to lightemitting materials for laser pigments or the like.

On the other hand, since organic compounds do not have carriersthemselves, they have essentially superior insulation properties.Therefore, with respect to the technique of electronics using electricalproperties of organic materials, the almost organic compounds have beenconventionally used as insulators such as insulating materials,protective materials, or covering materials.

However, there is means for applying large amounts of current to theorganic material that is essentially insulators. The means isincreasingly coming into practical use in the electronics field. It canbe broadly divided into two categories.

One of the means, as represented by conductive polymers, is that anacceptor (electron acceptor) or a donor (electron donor) is doped togive carriers to the n-conjugate system organic compound (Reference 1:Hideki Shirakawa, Edwin J. Louis, Alan G. MacDiamid, Chwan K. Chiang,and Alan J. Heeger, “Synthesis of Electrically Conducting OrganicPolymers: Halogen Derivatives of Polyacetyrene, (CH)_(x)”, Chem. Comm.,1977, 16, 578-580). Since the carriers expand to a certain area withincreased the amount of doping, the dark conductivity will also risealong with this, so that large amounts of current will become flow inthe organic material.

A part of the means for applying current to the organic material bydoping an acceptor or a donor to improve the dark conductivity hasalready been applied in the electronics field, for example, arechargeable secondary battery using polyaniline or polyacene, or anelectric field condenser using polypyrrole.

The other means for applying large amounts of current to the organicmaterial is utilization of an SCLC (Space Charge Limited Current). TheSCLC is the current that starts to flow by injecting and transferring aspace charge from the outside. The current density of the SCLC isexpressed by Child's Law, i.e., Formula 1 in the following. In theformula, J denotes current density, ∈ denotes relative permittivity, ∈₀denotes permittivity of vacuum, μ denotes carrier mobility, V denotes avoltage, and d denotes a distance to which the voltage V is applied:

J=9/8·∈∈₀ μ·V ² /d ³

Note that Formula 1 that expresses the SCLC does not assume at allcarrier-trap generated when the SCLC flows. The electric current limitedby carrier-trap is referred to as TCLC (Trap Charge Limited Current) andin proportion to power of the voltage. The rate of both SCLC and TCLCare determined by bulk. Therefore the SCLC is regarded the same as TCLChereinafter.

Here, for comparison, the current density when Ohm current flowsaccording to Ohm's Law is shown in Formula 2. σ denotes a conductivity,and E denotes an electric field strength:

J=σE=σ·V/d  Formula 2

In Formula 2, since the conductivity σ is expressed as σ=neμ (where ndenotes a carrier density, and e denotes an electric charge), thecarrier density is included in the factors controlling the amount ofcurrent. Therefore, unless increase of the carrier density by doping asdescribed above is attempted to an organic material having a certaindegree of carrier mobility, the Ohm current will not flow in the organicmaterial in which carriers hardly exist usually.

However, as shown in Formula 1, the determination factors of SCLC arethe permittivity, the carrier mobility, the voltage, and the distance towhich the voltage is applied. The carrier density is irrelevant. Inother words, it is possible to inject a carrier from the outside and toapply the current to the organic material even an organic material is aninsulator having no carriers by making the distance d sufficiently smalland by using a material having significant carrier mobility

When this means is used, the amount of current in the organic materialis as much as or more than that of a common semiconductor. Thus, anorganic material with high carrier mobility μ, in other words, anorganic material capable of transporting potentially a carrier, can bereferred to as an “organic semiconductor”.

Incidentally, organic electroluminescent devices (hereinafter, organicEL devices) achieve a striking prosperity in recent years asphotoelectronic devices which utilize both photonics and electricalqualities of functional organic materials among organic semiconductordevices which use the SCLC.

The most basic structure of the organic EL device was reported by W.Tang, et al. in 1987 (Reference 2: C. W. Tang and S. A. Vanslyke,“Organic electroluminescent diodes”, Applied Physics Letters, Vol. 51,No. 12, 913-915 (1987)).

The device reported in Reference 2 is a type of diode element in whichelectrodes sandwich an organic thin film to have a total thickness ofapproximately 100 nm that is formed by laminating a hole-transportingorganic compound and an electron-transporting organic compound. For theelectron-transporting compound, a light emitting material (fluorescentmaterial) is used. By applying voltage to the device, light-emission canbe extracted to outside as a light emitting diode.

The light-emission mechanism is considered as follows. By applying thevoltage to the organic thin film sandwiched by the electrodes, the holeand the electron injected from the electrodes are recombined inside theorganic thin film, and formed to be an excited molecule (hereinafter,referred to as a “molecular exciton”), and then, light is emitted whenthis molecular exciton returns to its base state.

Note that, singlet and triplet excitons formed by the organic compoundcan be utilized. Since the base state is normally the singlet state, thelight emission from the singlet excited state is referred to asfluorescent light, and the light emission from the triplet excited stateis referred to as phosphorescent light. In this specification, the lightemission from either excited states will be described.

In the above-described organic EL device, the organic thin film isnormally formed into a thin film to have a thickness of about 100 to 200nm. Further, since the organic EL device is a self-luminous device inwhich light is generated in the organic thin film itself, a backlightthat is used in a conventional liquid crystal display is not necessary.Therefore, the organic EL device has a great advantage of being able tobe manufactured to be ultrathin and lightweight.

Further, in the thin film having a thickness of about 100 to 200 nm, forexample, the amount of time for injecting and recombining of carriers isapproximately several tens of nanoseconds taking into consideration ofthe carrier mobility of the organic thin film. Even if the process ofcarrier's recombination and light emission, light emission can beachieved within on the order of microseconds. Therefore, extremely quickresponse time can be included in advantages of the organic thin film.

Because of the above-mentioned properties of thin and lightweight, thequick response time, and the like, the organic EL device is attracted anattention as a next generation flat panel display device. Further, sincethe organic EL display has a high level of visibility from its propertyof self-luminous and a broad visible range, the organic EL device isexpected to be used for display screens of portable devices.

An organic EL device is the device that utilizes means of applying SCLCto an organic semiconductor, but the SCLC intensifies the deteriorationof the organic semiconductor function. As to the organic EL device, itis known that the device lifetime (half-life of the luminance) isreduced inversely proportional to the initial luminance, in other words,the amount of current flowing. (Reference 3: Yoshiharu SATO, “The JapanSociety of Applied Physics/Organic Molecular Electronics andBioelectronics”, vol. 11, No. 1 (2000), 86-99).

In view of the foregoing, above-mentioned deterioration can be reducedby improving the current efficiency (luminance generating depending onthe electric current), since the necessary amount of electric current toachieve a certain luminance can be reduced. Thus, the current efficiencyis an important factor for an organic device in view of the devicelifetime, not to mention the power consumption.

However, an organic EL device has a problem with respect to the currentefficiency. As mentioned above, the light emission mechanism of theorganic EL device is that light is converted by recombination of theinjected hole and electron with each other. Therefore, in theory, it ispossible to extract at most one photon from the recombination of onehole and one electron, and it is impossible to extract a plurality ofphotons therefrom. That is, the internal quantum efficiency (the numberof emitted photons depending on injected carriers) should be at most 1.

However, in reality, it is difficult even to bring the internal quantumefficiency close to 1. For example, in the case of the organic EL deviceusing the fluorescent material as the luminant, the statisticalgeneration ratio of the singlet excited state (S*) and the tripletexcited state (T*) is considered to be S*:T*=1:3. Therefore, thetheoretical limit of the internal quantum efficiency is 0.25. (Reference4: Tetsuo TSUTSUI, “Textbook of the 3rd seminar at Division of OrganicMolecular Electronics and Bioelectronics, The Japan Society of AppliedPhysics” (1993), 31-37). Furthermore, as long as the fluorescent quantumyield from the fluorescent material is not φ_(f), the internal quantumefficiency will be decreased even lower than 0.25.

In recent years, there has been an attempt to bring the theoreticallimit of the internal quantum efficiency close to 0.75 to 1 by usingphosphorescent materials obtained from the light emission of the tripletexcited state. The internal quantum efficiency has been actuallyachieved exceeding that of the fluorescent material. However, the rangeof material choice is unavoidably restricted since a phosphorescentmaterial having high phosphorescent quantum efficiency φ_(p) should beused. That is caused by that the organic compounds that can releasephosphorescent light at room temperature are extremely scarce.

For this reason, as a means for improving the inferiority of the currentefficiency of a device, the concept of a charge generation layer wasreported in recent years (Reference 5: M. Herrmann, Junji KIDO, “49thJapan Society of Applied Physics and Related Societies” p. 1308,27p-YL-3 (March 2002)).

The concept of a charge generation layer is described as illustrated inFIGS. 7A-B. FIGS. 7A-B are frame formats of the organic EL devicedisclosed in Reference 5 that is formed by laminating an anode, an firstelectroluminescent layer, a charge generation layer, a secondelectroluminescent layer, and a cathode. Note that theelectroluminescent layer (hereinafter, an EL layer) is a layer includingan organic compound that can emit light by injecting carriers. Inaddition, the charge generation layer does not connect to an externalcircuit and serves as a floating electrode.

In such an organic EL device, when voltage V is applied to the regionbetween the anode and the cathode, electrons are injected to the firstEL layer from the charge generation layer and holes are injected to thesecond EL layer from the charge generation layer, respectively. Whenseen from the external circuit, holes are moving from the anode to thecathode and electrons are moving from the cathode to the anode (FIG.6A). However, it can be also seen that both holes and electrons from thecharge generation layer are moving in the reverse direction (FIG. 6B),so that carriers are recombined in both of the first EL layer and thesecond EL layer, and light is generated. In that case, if the current Iis flowing, both of the first EL layer and the second EL layer canrelease photons depending on the amount of current I, respectively.Therefore, such organic EL device have the advantage of releasing twotimes amount of light by the same amount of current compared to anorganic EL device having only one layer. (However, two times or moreamount of voltage is needed compared to the organic EL device havingonly one layer).

In the organic EL device employing such a charge generation layer, thecurrent efficiency can be improved significantly by laminating a numberof EL layers. (However, the structure requires several times or moreamount of voltage). Thus, in theory, the device lifetime can be expectedto be improved along with the improvement of the current efficiency.

However, when the current efficiency is tried to be improved using acharge generation layer, it is required that a number of EL layersshould be laminated and the fabricating process become complicated.Accordingly, the partial defect possibility such as a pinhole isincreased. Therefore another defects such as the dispersion of eachelement, the short-circuit of elements, and the like are apt to becaused. That is, the problem may be occurred with the yield of devicesthough the essential reliability of the device is improved according toimproving the current efficiency.

SUMMARY OF THE INVENTION

The inventor of the present invention considered in his dedicated studythe means that can solve above-mentioned problems by improving theorganic EL device including a charge generation layer (the inventor ofthe present invention refers to the charge generation layer as a bipolarcarrier generation layer). The basic structure thereof is illustrated inFIG. 1.

FIG. 1 is an organic EL device comprises an electroluminescent film 103between a first electrode 101 and a second electrode 102. Theelectroluminescent film 103 contains an organic compound capable ofcausing an electroluminescence. In the organic EL device, a bipolarcarrier generation layer 104 provided as a floating electrode isembodied in the electroluminescent film 103, an insulating layer 105 a(afirst insulating layer) is formed between the first electrode 101 andthe electroluminescent film 103. In addition, another insulating layer105 b(a second insulating layer) is formed between the second electrode102 and the electroluminescent film 103. In the case shown in FIG. 1,the bipolar carrier generation layer 104 is only provided as a singlelayer. Thus, the electroluminescent film 103 is divided into a firstelectroluminescent layer 103-1 and a second electroluminescent layer103-2 through the bipolar carrier generation layer 104. The wholestructure of the electroluminescent film 103 is sandwiched between theinsulating layer 105 a and the insulating layer 105 b.

By the way, the organic EL device shown in FIG. 1 has only one bipolarcarrier generation layer 104. Alternatively, it may have two or morebipolar carrier generation layers. For instance, as shown in FIG. 2, theorganic EL device may be constructed of electroluminescent layers 103-1to 103-n and bipolar carrier generation layer 104-1 to 104-m (wherein mdenotes an integer number of 1 or more, and n=m+1), which are arrangedin an alternate manner.

At this time, in the organic EL device shown in FIGS. 1 and 2 can bedesigned such that the insulating layers are thickened sufficiently toprevent carrier injections respectively from the first and secondelectrodes. In this case, the organic EL device is activated by an ACdrive as the carriers are injected only from the bipolar carriergeneration layer. In this case, therefore, a short circuit of the devicecan be prevented very effectively and the device excellent in a yield ordrive stability can be offered.

In a first aspect of the present invention, therefore, an organicelectroluminescent device having a first electrode, a second electrode,and an electroluminescent film containing an organic compound capable ofcausing an electroluminescence and being arranged between the firstelectrode and the second electrode, comprises: a bipolar carriergeneration layer, which is a floating electrode, is embedded in a theelectroluminescent film; an insulting film between the first electrodeand the electroluminescent film, which prevents a carrier injection fromthe first electrode to the electroluminescent film; and an insulatingfilm between the second electrode and the electroluminescent film, whichprevents a carrier injection from the second electrode to theelectroluminescent film.

In a second aspect of the present invention, an organicelectroluminescent device having an electroluminescent film containingan organic compound capable of causing an electroluminescence and beingarranged between a first electrode and a second electrode, comprises: abipolar carrier generation layer, which is a floating electrode, isembodied in the electroluminescent film; an insulting film between thefirst electrode and the electroluminescent film; and an insulating filmbetween the second electrode and the electroluminescent film, whereinthe organic electroluminescent device is driven by an alternatingcurrent bias.

Furthermore, considering that the organic electroluminescent device isdriven by an alternating current bias, the electroluminescent film maypreferably contain a layer having bipolar property. Alternatively, theelectroluminescent film includes an organic compound havingelectron-transporting property and an organic compound havinghole-transporting property in combination with each other to form abipolar mixed layer. By the way, the organic compound having bipolarproperty may be preferably a high molecular compound having aπ-conjugated system or a σ-conjugated system on the ground of simplyforming a film.

Furthermore, as a bipolar carrier generation layer, from the point oftransparency, it is preferable to contain an organic compound. In thiscase, for expressing a high function as a bipolar carrier generationlayer, it is preferable to contain at least one of an acceptor or adonor. More preferably, both the acceptor and donor for the organiccompound may be contained in the bipolar carrier generation layer.

In the organic EL device of the present invention, the bipolar carriergeneration layer should have sufficient carrier. Therefore, in anotheraspect of the present invention, the organic electroluminescent devicemay comprise the bipolar carrier generation layer having an electricconductivity of 10⁻¹⁰ S/m or more.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a view showing a basic structure according to the presentinvention;

FIG. 2 is a view showing a basic structure according to the presentinvention;

FIG. 3 is a view showing an organic EL device according to the presentinvention;

FIGS. 4A-C are views showing working mechanisms;

FIG. 5 is a view showing an organic EL device according to the presentinvention;

FIGS. 6A-C are views showing examples of structures of bipolar carriergeneration layers;

FIG. 7A and FIG. 7B are views showing organic EL device includingconventional charge generation layers;

FIG. 8 is a view showing a relationship between voltage and luminance inEmbodiment 4; and

FIG. 9 is a view showing AC drive characteristics in Embodiment 4.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, embodiments of the present invention will be described indetail while giving the working mechanism of and concrete configuration.Here, in an organic electroluminescent device (hereinafter, simplyreferred to as an organic EL device), one of two electrodes may betransparent so as to extract a luminescent outside from the organic ELdevice. Therefore, the present invention is not only limited to theconfiguration of the conventional device in which a transparentelectrode is formed on a substrate to extract the emission of light fromthe substrate side through the transparent electrode, actually, but alsoanother configuration of the device in which the emission of light isextracted from the side opposite to the substrate, or the configurationof the device in which the emission of light is extracted from the bothsides of the electrode.

At first, the working mechanism of the organic EL device of the presentinvention will be described with reference to FIGS. 3 and 4A-C. FIG. 3is an organic EL device of the present invention in which an AC powersupply is connected to the first electrode 101 and the second electrode102 shown in FIG. 1. In this figure, the same structural components asthose of FIG. 1 are denoted by the same reference numerals as those ofFIG. 1. In addition, a luminous body having bipolar property is used aseach of the first electroluminescent layer 103-1 and the secondelectrode electroluminescent layer 103-2. Furthermore, the potential ofthe first electrode is defined as V₁ and the potential of the secondelectrode is defined as V₂.

When the device is applied with an AC voltage, at first, at the time ofimmediately after the application of the bias of V₁>V₂, electrons movefrom the bipolar carrier generation layer 104 to the first electrode101, while holes move toward the second electrode 102. In each case,they are finally injected into the electroluminescent film 103 (FIG.4A).

On the other hand, as the insulating layers 105 a and 105 b are present,there is no chance to inject the carriers into the electroluminescentfilm 103 from the first electrode 101 and the second electrode 102.Therefore, the carriers injected from the bipolar carrier generationlayer are not recombined, so that they will accumulate in the boundarybetween the insulating layer 105 a and the electroluminescent film 103and in the boundary between the insulating layer 105 b and theelectroluminescent film 103 (FIG. 4B), respectively.

As the voltage being applied is an alternating current bias, immediatelyafter that, the voltage (V₁<V₂) is applied on the device. At this time,from the bipolar carrier generation layer 104, the carriers are injectedin the direction opposite to the case in FIG. 4A, while the carriersaccumulated in FIG. 4B flow to the bipolar carrier generation layer 104(FIG. 4C). As a result, just as in the case of the organic EL device inwhich the conventional bipolar carrier generation layer is used (thepreliminary report for the 49th Spring Meeting of the Japan Society(March, 2002), p. 1308, 27p-YL-3), the carriers are recombined in thefirst electroluminescent layer 103-1 and the second electroluminescentlayer 103-2, resulting in light emission from there.

The present organic EL device is different from the device disclosed inthe above non-patent reference 5 is that the injection of carriers isonly performed from the bipolar carrier generation layer being embeddedin the inside but not from the outside electrode as an insulating layer105 a and an insulating layer 105 b, are arranged in the device. Thatis, only the apparent AC flows (behavior seemingly just like intrinsicEL is shown). This can protect the short circuit of the device or thelike easily and it is very useful.

Furthermore, the device of the present invention does not generate leakcurrent because of the presence of the insulating layers 105 a and 105b. Therefore, it is also one of the features that improvement inefficiency is expected more.

Furthermore, this invention can also be considered as a multilayer asshown in FIG. 2. The example (namely, the example in the case of m=2 andn=3) in which two bipolar carrier generation layers are inserted isshown in FIG. 5. In FIG. 5, the same reference numerals as those of FIG.2 are used. In addition, the working mechanism of this example wassubstantially the same one as that of FIG. 3 or 4A-C, except of thefollows. That is, firstly (the moment that bias was impressed at theunbias condition), carriers were already recombined to causeillumination in the second electroluminescent film 203-2 (on the otherhand, in the device of FIG. 3 mentioned previously, carriers are onlyaccumulated at the bias was firstly impressed).

Furthermore, the waveform of the above described alternating currentbias may be preferably sine wave, square wave, and triangle wave.However, the present invention is not limited to these waveforms. Themaximum voltage may be preferably 300 Volts or less.

In the above description, the principle of operation of this inventionwas described. In the following description, we will describe thepreferable configurations of the bipolar carrier generation layer to beused in the present invention and the preferable configuration of theelectroluminescent film. However, the present invention is not limitedto such a configuration.

The bipolar carrier generation layer may be, for example, a metal thinfilm, a metal-oxide thin film, an organic conductive thin film, or acombination thereof. For instance, in the non-patent reference 5, thereis disclosed a laminate prepared by laminating a metal oxide (ITO) on anorganic conductive thin film (Cs-doped BCP). In addition, on the bothsides of the bipolar carrier generation layer, an inorganic dielectricthin film such as LiF, a metal oxide such as Li oxide, an alkali metalor an organic thin film layer including alkaline earth metal ion, or thelike is provided as a cathode-side buffer layer. On the other hand, asan anode-side buffer layer, copper phthalocyanine may be used.

Furthermore, if it takes into consideration that the element of thepresent invention is driven by an alternating current bias, the bipolarcarrier generation layer should be designed such that both carriers ofholes and electrons can be injected. One of examples of such aconfiguration is shown in FIGS. 6A-C.

As shown in FIG. 6A, when the bipolar carrier generation layer 601 isformed from a single material, a semiconductor (e.g., an intrinsicsemiconductor) having a wide band gap in which electrons are located ina conductor and holes are located in a valence band, a redox polymerwhich can perform both oxidation and reduction can be considered. Inaddition, the reference numerals 610 and 611 in FIGS. 6A-C denoteelectroluminescent layers.

The concrete examples of the semiconductors having wide band gapsinclude III-group-N compounds such as GaN, AlN, BN, AlGaN, InGaN, andInAlGaN, II-VI group compounds ZnS, MgS, ZnSe, MgSe, ZnMgSSe, CdS, ZnO,and BeO, diamond, SiC, ZnGaSSe, CaF₂, and AlP. Furthermore, redoxpolymers include emeraldine base polyaniline (EB-PAni).

Here, as a bipolar carrier generation layer 601, it is effective to usean organic conductive body. For instance, there is a means for mixing ap-type organic semiconductor and an n-type organic semiconductor. Therepresentative examples of the p-type organic semiconductor may include,for example, copper phthalocyanine (abbrev., CuPc) having the followingstructural formula (1), and other metal phthalocyanine, non-metalphthalocyanine, or the like may be applied. The representative examplesof the n-type organic semiconductor may include, for example, F₁₆-CuPCor the like represented by the following structural formulas (2), or3,4,9,10-perylene tetra-carboxylic acid derivatives or the likerepresented by the general formulas (3) (abbrev., PV), (4) (abbrev.,Me-PTC), and (5) (abbrev., PTCAD).

Furthermore, there is another method using an organic conductor havingconductivity by preparing a charge-transfer complex as a mixture of theacceptor (electron acceptor) of the organic compound and the donor(electron donor) of the organic compound. The charge transfer complexestend to be crystallized and some of them show poor film formability.However, since the bipolar carrier generation layer of the presentinvention may be faulted in the shape of a thin layer or a cluster (sothat carriers can be injected), there is no substantial problem.

A representative example of the acceptor is TCNQ or a derivative thereofrepresented by the structural formula (6) below or a nickel complexrepresented by the structural formula (7) below. In addition, a typicalexample of the donor is a TTF or a derivative thereof represented by thestructural formula (8).

As another example of the organic conductor, there is a technique ofimparting a dark conductivity to an organic semiconductor by doping withan acceptor or a donor. As an organic semiconductor, an organic compoundhaving a n-conjugated system, as exemplified by a conductive highpolymer, may be used. Furthermore, in addition to the examples describedabove, the acceptor may be a Lewis acid such as iron(III) chloride or ahalogen compound (the Lewis acid can serve as an acceptor). As thedonor, in addition to the examples described above, a Lewis base such asan alkali metal or an alkaline earth metal may be used (a Lewis base canserve as a donor).

Although the example that constitutes a bipolar carrier generation layerfrom a single layer was described above. More preferably, there isanother technique of constituting a bipolar carrier generation layerfrom two or more materials, for example, as shown in FIG. 6B and FIG.6C.

FIG. 6B illustrates the configuration in which a bipolar carriergeneration layer 601 is constructed such that a conductive film 602 issandwiched between electroluminescent layers 610 and 611 through anintrinsic semiconductor 603. In such device structure, carriers can beinjected by applying either plus or minus bias thereto. Here, theintrinsic semiconductor 603 may preferably be brought into ohmic contactwith the conductive film 602. Furthermore, the conductive film 602 maybe a metal, or may be various kinds of inorganic compound conductors ororganic conductors described above. Furthermore, instead of theintrinsic semiconductor 603, it may be a redox polymer or an organicconductor.

FIG. 6C is the configuration of the bipolar carrier generation layer 601in which the cluster-like electron injection region 605 is provided inthe upper and lower sides of the conductive film 604 having a large workfunction. Such a construction allows the injection of holes from theconductive film 604 and electrons from the electron-injection region, acarrier can be injected whichever bias. As the conduction film 604having a large work function, ITO, Au, or the like can be considered.Alternatively, the organic conductors described above may be used. Theclustered electron injecting region 605 may be formed by making theconventional electron injecting material into a cluster shape. In thiscase, the conventional electron injecting material may be AL:Li alloy, ametal such as Ca, an inorganic electron injecting material such as LiF,an LiF, an organic compound having a large electron affinity.

It is also possible to make the configuration of FIG. 6C reversely fromone described above. That is, cluster-like hole-injecting regions 605are formed on the upper and lower sides of the conductive film 604having a small work function. In this case, the conductive film 604having a small work function may be an Al:Li alloy, Ca, or one of otherorganic conductors as described above. The cluster-like hole-injectingregion 605 may be formed by making the conventional hole-injectingmaterial into a cluster shape. In this case, the conventionalhole-injecting material may be a metal such as Au or ITO, or aninorganic compound conductor, or an organic compound having acomparatively small ionization potential.

Next, hereinafter, the configuration of the electroluminescent layerwill be exemplified. Typically, the electroluminescent layer may beconstructed of any structural component generally used in the organic ELdevice structure. However, considering the activation of the device withalternating current bias, it is preferable to form electroluminescentlayer having bipolar properties.

As a method for obtaining a bipolar electroluminescent layer, onecomprises the steps of mixing a hole-transporting material and anelectron-transporting material to form a layer having bipolarproperties. Available hole-transporting materials include aromatic-aminecompounds (i.e., having benzene-ring to nitrogen bonds) which have beenwidely used in the art, such as 4,4′-bis(diphenyl amino)-biphenyl(abbreviated name: TAD) and derivatives thereof, 4,4′-bis[N-(3-methylphenyl)-N-phenyl-amino]-biphenyl (abbreviated name: TPD) and4,4′-bis [N-(1-naphthyl)-N-phenyl-amino]-biphenyl (abbreviated name:α-NPD). In addition, starburst-type aromatic amine compounds such as4,4′,4″-tris (N,N-diphenyl-amino)-triphenylaminine (abbreviated name:TDATA), 4,4′,4″-tris[N-(3-methylphenl)-N-phenyl-amino]-triphenylamine(abbrev., MTDATA) may be used. Furthermore, as an electron-transportingmaterial, any of metal complexes have been generally used, such as metalcomplexes having quinoline skeletons or benzoquinoline skeletonsincluding tris (8-quinolinolato) aluminum (abbrev., Alq), tris(4-methyl-8-quinolinolato) aluminum (abbrev., Almq), and bis(10-hydroxybenzo[h]-quinolinato) beryllium (abbrev., Bebq), and a mixedligand complex such asbis(2-methyl-8-quinolinolato)-(4-hydroxy-biphenyl)-aluminum (abbrev.,BAlq). Furthermore, metal complexes having oxazole or thiazole ligandssuch as zinc bis[2-(2-hydroxyphenyl)-benzoxazorato] (abbrev., Zn(BOX)₂),and zinc bis[2-(2-hydroxyphenyl)-benzothiazorato] (abbrev., Zn(BTZ)₂)Furthermore, in addition to the metal complexes, materials havingelectron-transporting properties include oxadiazol derivatives such as2-(4-biphenyl)-5-(4-tert-buthylphenyl)-1,3,4-oxadiazole (abbrev., PBD)and 1,3-bis [5-(p-tert-butylphenyl)-1,3,4-oxadiazole-2-il]benzene(abbrev., OXD-7), triazole derivatives such as3-(4-tert-butylphenyl)-4-phenyl-5-(4-biphenyl)-1,2,4-triazole (abbrev.,TAZ),3-(4-tert-butylphenyl)-4-(4-ethylphenyl)-5-(4-biphenylyl)-1,2,4-triazole(abbrev., p-EtTAZ), and phenanthroline derivatives such asbathophenanthroline (abbrev., BPhen) and batho-cuproine (abbrev., BCP)have an electron-transporting property.

Furthermore, many of the EL device materials using high molecularcompounds show bipolar properties, so that they can be preferably used,specifically including polyparaphenylene polymers such as poly(2,5-dialkoxy-1,3-phenylene) (abbrev., RO-PPP), polyparaphenylenevinylene polymer such as poly (2,5-dialkoxy-1,4-phenylene vinylene)(abbrev., RO-PPV), and polyfluorene polymer such aspoly(9,9-dialkylfluorene) (abbrev., PDAF).

As the first electrode and second electrode, any conductive material maybe used. Aluminum, chromium, titanium, or the like may be used. Amongthem, preferably, a transparent conductive film such as ITO may be usedfor at least one of these electrodes for the need of transparency. Inaddition, as the insulating layer, an inorganic insulator such asaluminum oxide or calcium fluoride or an insulating organic materialsuch as polyparaxylylene may be used. In this case, it is noted that atleast the insulating layer on the light-emitting side should havetransparency.

Color mixture of each electroluminescent layer is carried out as adifferent luminescent color to allow white luminescence. Furthermore,therefore, the organic EL device of the present invention will be alsoapplicable to white luminescence with high efficiency and long devicelife. In addition, the application not only to display but also tolighting or the like will be also considerable.

Embodiment 1

An organic EL device of the present invention that is fabricated by thevapor deposition will be specifically described in this embodiment.First, ITO is deposited to have a thickness of 100 nm as a firstelectrode on a glass substrate by vapor deposition, and oxide aluminumis deposited thereon to have a thickness of 300 nm as an insulatinglayer by EB vapor deposition.

Next, N,N′-bis(3-methylphenyl)-N,N′-diphenyl-benzidine (abbrev., TPD) asa hole transporting material and tris (8-quinolinolato) aluminum(abbrev., Alq) as an electron transporting material are co-deposited at1:4 weight ratio to form a bipolar first electroluminescent layer tohave a thickness of 100 nm. Here,4-dicyariomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran(abbrev., DCM) as a fluorescent pigment is doped to the center portionas much as 60 nm (between 20 to 80 nm from bottom of the thickness) tohave weight ratio that TPD: Alq: DCM=1:4: 0.05.

After the first electroluminescent layer is formed in such a way,metallic aluminum is formed to have a thickness of 30 nm as a bipolarcarrier generation layer.

Thereafter, a second electroluminescent layer is continuously formed inexactly the same way as the first electroluminescent layer withoutbreaking a vacuum. Moreover, oxide aluminum is deposited to have athickness of 300 nm as an insulating layer by EB vapor deposition.Lastly, aluminum is deposited to have a thickness of 100 nm as a secondelectrode. Then, an organic EL device of the present invention can beformed.

Embodiment 2

An organic EL device of the present invention fabricated by wet coatingwill be specifically described in this embodiment. First, poly(vinylphenol) is coated by spin coating to have a thickness of 200 nm as aninsulating layer on the glass substrate on which ITO is formed to haveapproximately 100 nm in thick as a first electrode. In addition, amaterial for solvent is isopropanol.

Second, poly(2-methoxy-5-(2-ethyl-hexoxy)-1,4-phenylenevinylene)(abbrev., MEH-PPV) is dissolved in dichloroethane, and coated 80 nm inthick by spin coating to form a first electroluminescent layer.

After the first electroluminescent layer is formed in such a way,aqueous solution of poly(ethylene dioxythiophene) doped with polystyrenesulfonic acid (abbrev., PEDOT/PSS) is spin coated to form a bipolarcarrier generation layer to have a thickness of 100 nm.

Thereafter, a second electroluminescent layer is continuously formed inexactly the same way as the first electroluminescent layer. Further,poly(vinyl phenol) is coated by spin coating to have a thickness of 200nm as an insulating layer. Lastly, aluminum is formed to have athickness of 100 nm as a second electrode. Then, an organic EL device ofthe present invention can be formed.

Embodiment 3

An organic EL device of the present invention fabricated by coating withpolymer composite films containing luminous pigments and bonding withoutusing vapor deposition will be specifically described in thisembodiment.

First, poly(vinyl phenol) is coated by spin coating to have a thicknessof 200 nm as an insulating layer on the plastic substrate (polyestersubstrate or polyimide substrate) on which ITO is formed 100 nm in thickas a first electrode. In addition, a material for solvent isisopropanol.

Next, dichloromethane solution prepared from 50 wt % polycarbonate asbinder, 29 wt % TPD as a hole transporting material, 20 wt %2,5-bis(1-naphthyl)-1,3,4-oxadiazole (abbrev., BND) as an electrontransporting material, 1.0 wt % coumarin 6 as a luminous pigment is spincoated on the insulating layer to form a first electroluminescent layerto have 100 nm in thick.

After the first electroluminescent layer is formed in such a way,polyaniline doped with camphor-10-sulfonic acid (abbrev.,PAni(CSA)_(0.5)) is formed as a bipolar carrier generation layer to havea thickness of 50 nm by spin-coating 1,1,1,3,3,3-hexafluoro-2-propanol(abbrev., HFIP) solution of PAni(CSA)_(0.5).

Then, dichloromethane solution prepared from 50 wt % polycarbonate asbinder, 29 wt % TPD as a hole transporting material, 20 wt %2,5-bis(1-naphthyl)-1,3,4-oxadiazole (abbrev., BND) as an electrontransporting material, 1.0 wt % coumarin 6 as a luminous pigment is spincoated on the insulating layer to form a second electroluminescent layerto have 100 nm in thick. Hereinafter, the substrate that is executed thedeposition so far is referred to as a “first electrode side substrate”.

In addition to above-mentioned substrate, poly(vinyl phenol) is coatedas an insulating layer to have a thickness of 200 nm on a plasticsubstrate on which ITO having same size is formed. Hereinafter, thesubstrate is referred to as a “second electrode side substrate”. For thedeposition of poly(vinyl phenol), isopropanol solution may be spincoated as same as the previous way.

Here, spacer film having 650 nm in thick is positioned on the peripheryportion of the first electrode side substrate prepared in advance, andthe second electrode side substrate is bonded to let the secondelectrode is inside of the substrate.

The bonded film substrate is putted on a stainless plate of a hot plate,and weighted by superimposing another stainless plate thereon, then,heated up to 80° C. as it is. The film substrate is cooled withweighting, and got it out of the stainless plate, then, fitted with alead wiring, and then, an organic EL device of the present invention iscompleted.

Embodiment 4

Iso-propanol solution of poly(4-vinyl phenol) is spin coated onto an ITOglass substrate to have a thickness of 200 nm. The film is dried at 60°C. in vacuum for 30 minutes. Then, an insulating film comprisingpoly(4-vinyl phenol) is formed.

Next, dichloromethane solution in which polyvinylcarbazole (64.3 mol. %)as a hole transporting material, 2.5-bis(1-naphthyl)-1,3,4-oxadiazole(BND) (35.1 mol. %) as an electron transporting material, and acoumarine-6dye (0.6 mol. %) as a light emission dye are dissolved isspin coated on the insulating film to have a thickness of 200 nm, anddried at 60° C. in vacuum for 30 minutes, then, a polymer layer isformed.

On top of that, iso-propanol suspension of ITO particles (average graindiameter 50 nm) is uniformly spread by spin coating. Further,dichloromethane solution in which polyvinylcarbazole (64.3 mol. %) as ahole transporting material, 2.5-bis(1-naphthyl)-1,3,4-oxadiazole (BND)(35.1 mol. %) as an electron transporting material, and a coumarine-6dye(0.6 mol. %) as a light emission dye are dissolved is spin coated tohave a thickness of 200 nm, and dried at 60° C. in vacuum for 1 hour,then, a polymer layer is formed. Iso-propanol solution of poly(4-vinylphenol) is spin coated thereon to have a thickness of 200 nm. The filmis dried at 60° C. in vacuum for 30 minutes. Then, an insulating filmcomprising poly(4-vinyl phenol) is formed. Lastly, an aluminiumelectrode is formed thereon to have a thickness of 60 nm by vapordeposition.

AC power generating sine wave is connected between the electrodes. ACvoltage is applied to the electrode (the drive frequency range is 1 kHzto 100 kHz). In the case that AC voltage is applied at drive frequency100 kHz, homogeneous green luminescence of coumarin pigments exactlywith the rectangular electrode shape can be observed at voltage 60V(peak voltage) viewing from the ITO electrode side. A measurement ofluminance with a luminance meter (Topcon BM-5A) shows 30 cd/m² atapplied voltage 180V. When the device is continuously applied 180V,since more voltage than 180V cannot applied for limitation of AC power,the device can continuously emit light with little luminance attenuationfor 1 hour. Even when the drive frequency is lowered to 1 kHz, luminancecan be observed.

FIG. 8 shows a relationship between voltage (illustrated with peakvoltage) at drive frequency 100 kHz and luminance. FIG. 9 shows theresult of time profile of luminance strength detected using aphotomultimeter measured simultaneously with applying voltage usingoscilloscope. The measurement result shows that luminance is generatedin synchronization with plus and minus peak voltages.

Embodiment 5

Iso-propanol solution of poly(4-vinyl phenol) is spin coated onto an ITOglass substrate to have a thickness of 200 nm. The film is dried at 60°C. in vacuum for 30 minutes. Then, an insulating film comprisingpoly(4-vinyl phenol) is formed.

Next, dichloromethane solution in which polyvinylcarbazole (64.3 mol. %)as a hole transporting material, 2.5-bis(1-naphthyl)-1,3,4-oxadiazole(BND) (35.1 mol. %) as an electron transporting material, and acoumarine-6dye (0.6 mol. %) as a light emission dye are dissolved isspin coated onto the insulating film to have a thickness of 200 nm, anddried at 60° C. in vacuum for 1 hour, then, a polymer composite filmlayer is formed.

On top of that, iso-propanol suspension of ITO particles (average graindiameter 50 nm) is uniformly spread by spin coating.

Further, dichloromethane solution in which polyvinylcarbazole (64.3 mol.%) as a hole transporting material, 2.5-bis(1-naphthyl)-1,3,4-oxadiazole(BND) (35.1 mol. %) as an electron transporting material, and acoumarine-6dye (0.6 mol. %) as a light emission dye are dissolved isspin coated thereon to have a thickness of 200 nm, and dried at 60° C.in vacuum for 1 hour, then, a polymer composite film layer is formed.

Then, the steps of spin coating iso-propanol suspension of ITO particleand spin coating dichloromethane solution for forming a polymercomposite film layer are respectively repeated twice.

Iso-propanol solution of poly(4-vinyl phenol) is spin coated thereon tohave a thickness of 200 nm. The film is dried at 60° C. in vacuum for 30minutes. Then, an insulating film comprising poly(4-vinyl phenol) isformed. Lastly, an aluminium electrode is formed thereon to have athickness of 60 nm by vapor deposition.

AC power generating sine wave is connected between electrodes. ACvoltage is applied to the electrode (the drive frequency range is 1 kHzto 100 kHz). In the case that AC voltage is applied at drive frequency100 kHz, homogeneous green luminescence of coumarin pigments exactlywith the rectangular electrode shape can be observed at voltage 70V(peak voltage) viewing from the ITO electrode side. A measurement ofluminance with a luminance meter (Topcon BM-5A) shows 25 cd/m² atapplied voltage 180V.

Embodiment 6

All of the elements of an organic EL device according to the presentinvention are fabricated by wet processing using polymer composite filmscontaining light emitting dye and bonding without using vapordeposition.

Iso-propanol solution of poly(4-vinyl phenol) is spin coated on apolyester substrate on which ITO is formed to have a thickness of 100 nmas a bottom electrode to have a thickness of 200 nm. Then, an insulatingfilm comprising poly(4-vinyl phenol) is formed.

Next, dichloromethane solution in which polyvinylcarbazole (64.3 mol. %)as a hole transporting material, 2.5-bis(1-naphthyl)-1,3,4-oxadiazole(BND) (35.1 mol. %) as an electron transporting material, and acoumarine-6dye (0.6 mol. %) as a light emission dye are dissolved isspin coated to have a thickness of 200 nm, and dried at 60° in vacuumfor 1 hour, then, a polymer composite film layer is formed.

On top of that, iso-propanol suspension of ITO particles (average graindiameter 50 nm) is uniformly spread by spin coating.

In addition to the substrate, a polyester substrate on which ITO isformed to have a thickness of 100 nm as a bottom electrode is prepared,and iso-propanol solution of poly(4-vinyl phenol) is spin coated thereonto have a thickness of 200 nm as an insulating film comprisingpoly(4-vinyl phenol). Further, dichloromethane solution in whichpolyvinylcarbazole (64.3 mol. %) as a hole transporting material,2.5-bis(1-naphthyl)-1,3,4-oxadiazole (BND) (35.1 mol. %) as an electrontransporting material, and a coumarine-6dye (0.6 mol. %) as a lightemission dye are dissolved is spin coated thereon to have a thickness of200 nm, and dried at 60° C. in vacuum for 1 hour, then, a polymercomposite film layer is formed.

Two fabricated polyester substrates are bonded together to let thespin-coated materials on the substrates face each other. Then, thebonded substrate is sandwiched by two glass plates, and weighted, then,heated as it is in an oven up to 80° C. for 30 minutes.

AC power generating sine wave is connected between two electrodes. ACvoltage is applied to the electrode (the drive frequency range is 1 kHzto 100 kHz). In the case that AC voltage is applied at drive frequency100 kHz, homogeneous green luminescence of coumarin pigments exactlywith the rectangular electrode shape can be observed at voltage 60V(peak voltage) viewing from the ITO electrode side. In this case,luminescence of same luminance can be observed from both top and bottomsurfaces. Even if the substrate is bended, there is no luminancetransition.

According to the present invention, the current efficiency can beimproved and an organic EL device having good yields, high reliability,and high can be provided.

1. An organic electroluminescent device comprising: a first electrode; asecond electrode; and an electroluminescent film containing an organiccompound capable of causing an electroluminescence and being providedbetween the first electrode and the second electrode, wherein a carriergeneration layer is embodied in the electroluminescent film, saidcarrier generation layer being a floating electrode; wherein a firstinsulting film is provided between the first electrode and theelectroluminescent film, said first insulting film preventing a carrierinjection from the first electrode to the electroluminescent film; andwherein a second insulating film is provided between the secondelectrode and the electroluminescent film, said second insulating filmpreventing a carrier injection from the second electrode to theelectroluminescent film. 2-9. (canceled)